Composition, curable composition, cured product, optical article, lens, glasses, antibacterial / antiviral agent, and resin composition

Abstract

The present invention provides a composition comprising: a first bismuth compound having bismuth and having at least one of an acryloyl group and a methacryloyl group; and a coordinating organic compound having an acid dissociation constant (pKa) of 1.5 or more. Further, the present invention provides: a curable composition containing the composition; a cured product of the curable composition; an optical article, a lens, a pair of glasses, and an antibacterial / antiviral agent, each of which contains the cured product; and a resin composition.

Description

Technical Field

[0001] The present invention relates to a composition, a curable composition, a cured product, an optical article, a lens, spectacles, an antibacterial / antiviral agent and a resin composition. Background Art

[0002] In response to the International Commission on Radiological Protection (ICRP)'s warning about the risk of radiation causing cataracts, Japan revised its regulations for preventing the hazards of ionizing radiation, lowering the limit on the equivalent dose to the lens of the eye for workers working with radiation from April 2021. This has further strengthened the call for workers working with radiation to effectively use appropriate eye protection materials to reduce risks.

[0003] Lead glass and lead acrylic, commonly used as a lightweight material, are the raw materials for shielding materials used for eye protection. However, lead is harmful to the environment and the human body, and there is a strong demand for lead-free alternatives in shielding materials based on inorganic glass or resin. Examples of lead substitutes include bismuth, barium, antimony, tin, and tungsten; research is underway on materials using bismuth. Bismuth has long been used in gastrointestinal medicine, is harmless to the human body, and offers radiation shielding capabilities comparable to lead, making it a suitable element for replacing lead.

[0004] In general, bismuth compounds have low solubility in organic solvents containing polymerizable monomers, and their use is restricted. In recent years, reports have been made on obtaining a cured product having sufficient transparency as an optical material by using a composition containing a bismuth compound and a free radical polymerizable monomer other than the bismuth compound, wherein the bismuth of the bismuth compound is bonded to a phosphate having a (meth) acryloyl group (see Patent Documents 1 and 2). The cured product has a high concentration of bismuth components dispersed in a resin matrix, and has excellent shielding capabilities not only for medical X-rays but also for shielding radiation such as beta rays, and can be used for radiation protection eyeglass lenses, shielding materials, screens, observation windows, and the like.

[0005] Bismuth compounds are also known to have antibacterial and antiviral properties and can be used as structural materials or coating materials with antibacterial / antiviral properties. However, transparency is not necessarily required for these applications.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2022 / 014591

[0009] Patent Document 2: International Publication No. 2019 / 177084 Summary of the Invention

[0010] Problems to be solved by the invention

[0011] The present invention aims to provide a composition and a curable composition with reduced odor, a cured product of the curable composition, an optical article, a lens, spectacles, an antibacterial / antiviral agent, and a resin composition comprising the cured product.

[0012] Solutions for solving problems

[0013] Specific means for solving the above-mentioned problems include the following embodiments.

[0014] <1> A composition comprising:

[0015] a first bismuth compound having bismuth and at least one of an acryloyl group and a methacryloyl group; and

[0016] A coordinating organic compound with an acid dissociation constant pKa of 1.5 or greater.

[0017] <2> The composition according to <1>, wherein the coordinating organic compound has an acid dissociation constant pKa of 2.0 to 15.0.

[0018] <3> The composition according to <1> or <2>, wherein a ratio M1 / M2 of a mass M1 of the first bismuth compound to a mass M2 of the coordinating organic compound is 4 or more and 4990 or less.

[0019] <4> The composition according to any one of <1> to <3>, wherein the coordinating organic compound comprises at least one selected from the group consisting of compounds having an imidazole skeleton, compounds having a pyrazole skeleton, compounds having a triazole skeleton, and compounds having a tetrazole skeleton.

[0020] <5> The composition according to any one of <1> to <4>, wherein the coordinating organic compound includes a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and an unsaturated bond.

[0021] <6> The composition according to any one of <1> to <5>, wherein the coordinating organic compound contains an unsaturated dicarboxylic acid.

[0022] <7> The composition according to any one of <1> to <6>, wherein the coordinating organic compound comprises an unsaturated carboxylic acid ester.

[0023] <8> The composition according to any one of <1> to <7>, wherein the coordinating organic compound comprises an unsaturated carboxylic acid anhydride.

[0024] <9> The composition according to any one of <1> to <8>, wherein the coordinating organic compound comprises an imidazole, 1-vinylimidazole, 1-allylimidazole, N-acetylimidazole, trimethylsilylimidazole, pyrazole, triazole, 1H-tetrazole, 1,2,3-benzotriazole, benzimidazole, allyl isonicotinate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, indole, carbazole, 2-methyl At least one compound selected from the group consisting of imidazole, 4-methylimidazole, 1,2-benzisothiazol-3(2H)-one, 2-isopropylimidazole, 1,2-dimethylimidazole, levomenthol, piperonal, triallyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, 2-(tert-butylamino)ethyl methacrylate, 4-acryloylmorpholine, triacryloylhexahydrotriazine, dimethylpyrazole, linalool, camphor, acrylic acid, methacrylic acid, maleic acid, acrylic anhydride, methacrylic anhydride, and maleic anhydride.

[0025] <10> The composition according to any one of <1> to <9>, wherein the first bismuth compound further has a phosphate bond.

[0026] <11> The composition according to any one of <1> to <10>, wherein the first bismuth compound further has a phenyl group.

[0027] <12> A curable composition comprising:

[0028] The composition according to any one of <1> to <11>; and

[0029] The first polymerizable compound has at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

[0030] <13> The curable composition according to <12>, wherein the total content of the first bismuth compound and the coordinating organic compound is 10% by mass or more and 90% by mass or less.

[0031] <14> A cured product comprising the curable composition according to <12> or <13>.

[0032] <15> An optical article comprising the cured product according to <14>.

[0033] <16> A lens comprising the cured product according to <14>.

[0034] <17> A pair of glasses comprising the lens described in <16>.

[0035] <18> An antibacterial / antiviral agent comprising the cured product according to <14>.

[0036] <19> A resin composition comprising bismuth and a (meth)acrylic resin,

[0037] The phenol content determined by gas chromatography-mass spectrometry using the polymerization inhibitor present inside as a reference was 10 ppm or less.

[0038] Effects of the Invention

[0039] According to the present invention, there can be provided a composition and a curable composition with reduced odor, a cured product of the curable composition, an optical article, a lens, spectacles, an antibacterial / antiviral agent including the cured product, and a resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a diagram showing the GC / MS spectrum of the cured product of Example 3. DETAILED DESCRIPTION

[0041] Hereinafter, specific embodiments to which the present invention is applied will be described in detail.

[0042] In this specification, the term "(meth)acryl" refers to both "acryl" and "methacryl", and the term "(meth)acrylate" refers to both "acrylate" and "methacrylate". The same applies to terms such as "(meth)acrylic acid".

[0043] Composition

[0044] The composition of this embodiment includes a first bismuth compound and a coordinating organic compound. The first bismuth compound contains bismuth and at least one of an acryloyl group and a methacryloyl group. The coordinating organic compound has an acid dissociation constant pKa of 1.5 or greater. Using the composition of this embodiment can produce a cured product with reduced odor. The reason for this is presumably as follows.

[0045] The solidified material containing the first bismuth compound sometimes contains impurities. These impurities are derived from, for example, the raw materials of the first bismuth compound and by-products generated when the first bismuth compound is manufactured. These impurities are difficult to completely remove during the purification operation and sometimes remain in the solidified material. These impurities remaining in the solidified material may cause the odor of the solidified material. The present inventors have conducted in-depth research and found that these impurities can be contained in the solidified material in the form of being coordinated on the bismuth of the first bismuth compound. That is, the bismuth element forms an atomic valence state of 0, 3 or 5 valence. In the composition of this embodiment, the bismuth of the first bismuth compound can also be reversibly changed to a state of 0, 3 or 5 valence. Furthermore, even for trivalent bismuth, it is 8-coordinated, so the impurities contained in the composition can be coordinated on the empty coordination site of bismuth, or the impurities can be coordinated as substituents. The present inventors have found that the impurities coordinated on bismuth will be freed from the bismuth over time and released into the atmosphere, which may cause odor.

[0046] For example, when a compound containing a phenyl ester moiety of phosphoric acid is used as a raw material for manufacturing the first bismuth compound, it undergoes partial hydrolysis during manufacturing, liberating phenol. The free phenol can coordinate with bismuth. This phenol is an important example of a byproduct that causes the aforementioned odor. The phenol contained in the first bismuth compound or the phenol contained in the solidified material containing the first bismuth compound can be analyzed using a headspace gas chromatography-mass spectrometer (GC / MS), and its volatilization amount can be easily quantified using a phenol gas detector tube.

[0047] As described above, the composition of this embodiment includes a first bismuth compound and a coordinating organic compound. Since the coordinating organic compound has an acid dissociation constant pKa of 1.5 or greater, it is believed that it can coordinate to bismuth preferentially over impurities. Therefore, in the composition of this embodiment, the amount of the first bismuth compound coordinated with impurities can be reduced. Therefore, if the composition of this embodiment is used, a solidified product with reduced impurities and reduced odor can be achieved. Even if the residual amount of byproducts that cause odor contained in the first bismuth compound is tens of ppm, the amount of volatile odorous substances in this embodiment can still be below 5 ppm, although it also depends on the characteristics of its molecules, and can be below the detection limit under optimal conditions.

[0048] Hereinafter, each component used in the composition of this embodiment will be described.

[0049] <First Bismuth Compound>

[0050] The first bismuth compound contains bismuth and at least one of an acryloyl group and a methacryloyl group. The first bismuth compound, because it contains bismuth, can be used as a radiation shielding material. Radiation includes electromagnetic radiation and particle radiation. Electromagnetic radiation includes X-rays and gamma rays. Particle radiation includes alpha rays, beta rays, neutron rays, and proton beams. Due to its excellent X-ray shielding capability, the first bismuth compound is particularly suitable for use as an X-ray shielding material and a shielding material for beta rays, which can generate X-rays.

[0051] The first bismuth compound has high solubility in a radically polymerizable compound having at least one radically polymerizable group selected from the group consisting of a nitrile group, an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group. Therefore, the use of the first bismuth compound can produce a curable composition containing a high concentration of bismuth and a cured product thereof. The first bismuth compound has superior solubility in radically polymerizable compounds compared to bismuth subsalicylate monomer.

[0052] The first bismuth compound may be in any form as long as it contains bismuth and a (meth)acryloyl group. For example, the bismuth and (meth)acryloyl groups may be bonded directly or through a bonding group. Examples of bonding groups include oxygen atoms, sulfur atoms, nitrogen atoms, and phosphate groups.

[0053] The first bismuth compound preferably also has a phosphate bond. In addition, the first bismuth compound is more preferably bismuth bonded to a first phosphate ester having a (meth) acryloyl group. Such a first bismuth compound tends to have a higher compatibility with various polymerizable compounds. The bonding form of bismuth and the first phosphate ester is not particularly limited and can be any of an ionic bond, a coordination bond, and a covalent bond. That is, the first bismuth compound can be a bismuth (Bi 3+ Or Bi 5+ ) is a phosphate or complex salt with the first phosphate ester as an anion, or it can be a phosphate compound or a complex.

[0054] The first bismuth compound may be a mono(meth)acrylate having one (meth)acryloyl group, a di(meth)acrylate having two (meth)acryloyl groups, a tri(meth)acrylate having three (meth)acryloyl groups, or a multifunctional (meth)acrylate having four or more (meth)acryloyl groups.

[0055] In the first bismuth compound, the first phosphate ester is represented by, for example, the following formula (2).

[0056]

[0057] In the above formula (2), Q 1 is a hydrogen atom or a methyl group. 1 Preferred is methyl.

[0058] Q 2 The carbon number of the alkyl group is preferably 1 to 6. The carbon number of the aryl group is preferably 5 to 8. The aryl group is preferably a phenyl group. The carbon number of the alkylene group in the (meth)acryloyloxyalkylene group is, for example, 1 to 10, preferably 1 to 3. The (meth)acryloyloxyalkylene group is preferably (meth)acryloyloxyethylene.

[0059] a 3 is 0 or 1. 3 When Q is 0, 2 The bonded oxygen atom is O － .

[0060] Q 3 It is a linear or branched alkylene group having 1 to 10 carbon atoms, or a linear or branched alkyleneoxyalkylene group having 1 to 10 carbon atoms.

[0061] In addition to the first phosphate, the first bismuth compound may be further bonded with other compounds. The bonding form between bismuth and other compounds may be any of an ionic bond, a coordination bond, and a covalent bond. That is, the first bismuth compound may be bismuth (Bi 3+ Or Bi 5+ ) as a cation and the first phosphate ester and other compounds as anions of the phosphate or complex salt, can also be a phosphate compound, can also be a complex.

[0062] Specific examples of other compounds include at least one selected from the group consisting of salicylic acid and (meth)acrylic acid.

[0063] To improve solubility in the radically polymerizable compound, the ratio of the first phosphate ester to the other compounds is preferably 0.1 to 10 moles of the other compounds per 1 mole of the first phosphate ester, more preferably 0.1 to 5 moles, even more preferably 0.1 to 1 mole, and particularly preferably 0.1 to 0.5 moles. When two or more first phosphates are present, the above range is based on the total number of moles of the first phosphates.

[0064] The first phosphate bonded to the bismuth can be confirmed by infrared (IR) analysis. That is, in the infrared analysis of the first bismuth compound, for example, at 1670 to 1700 cm －1 If a peak is observed, it can be said that the first phosphate is bonded to the bismuth. This peak is considered to be a characteristic peak of Bi-OP stretching vibration. This peak is not observed in bismuth before bonding or in the first phosphate.

[0065] The IR spectrum is measured using, for example, Spectrum One manufactured by PerkinElmer, by an ATR method with single reflection and four-time accumulation.

[0066] In addition, the number of bonds of salicylic acid or (meth) acrylic acid, and each phosphate in the first bismuth compound can be confirmed by combining NMR (nuclear magnetic resonance spectroscopy), MALDI-TOF-MS (matrix-assisted laser desorption ionization time-of-flight mass spectrometry), XPS (X-ray photoelectron spectroscopy) and elemental analysis based on EDS (energy dispersive X-ray spectroscopy).

[0067] 1 H-、 31 In the P-NMR measurement, a nuclear magnetic resonance apparatus (JNM-ECA400II manufactured by JEOL Ltd.) was used, deuterated acetone was used as a solvent, and the measurement was performed at a sample concentration of 1% by mass.

[0068] XPS measurement was performed using an X-ray photoelectron spectrometer (ESCA5701ci / MC manufactured by ULVAC-PHI, INCORPORATED) and a monochromated Al-Kα (14 kV-330 W) X-ray source. The sample was crushed in an agate mortar and fixed to a substrate with carbon tape. The powder was then introduced into the measurement chamber and measured.

[0069] The first bismuth compound preferably further has a phenyl group. The first bismuth compound having a phenyl group tends to have high compatibility with the radical polymerizable monomer. For example, the presence of a phenyl group in the first bismuth compound can be confirmed by FT-IR (Fourier Transform Infrared Spectroscopy).

[0070] The first bismuth compound is, for example, a phosphate or complex salt represented by the following formula (1).

[0071]

[0072] In the above formula (1), Q 1 , Q 2 , Q 3 and a 3 Same as the above formula (2).

[0073] In the above formula (1), X is (meth)acrylic acid represented by the following formula (1a) or salicylic acid represented by the following formula (1b). In formula (1a), R is a hydrogen atom or a methyl group. X is preferably salicylic acid represented by the following formula (1b).

[0074]

[0075]

[0076] a 1 A number greater than or equal to 0 and less than or equal to 1.

[0077] a 2 It is a number greater than or equal to 0.1 and less than or equal to 3.

[0078] a 1 +a 2 A number greater than 2 and less than 3.

[0079] The fact that the first bismuth compound has the structure represented by the above formula (1) can be confirmed by, for example, detecting the protonated molecular ion or sodium adduct ion of the compound in MALDI-TOF-MS measurement. 1 is a number from 1 to 2, X is salicylic acid, a 2 A number from 1 to 3, Q 1 is methyl, Q 2 is a methacryloyloxyalkyl group, Q 3 When a compound having a linear alkyl group having 2 carbon atoms is measured, a protonated ion of m / z = 667 is detected.

[0080] MALDI-TOF-MS measurements were performed using a Bruker rapiflex TOF / TOF, using CHCA (α-cyano-4-hydroxycinnamic acid), DIT (Dithranol), and DHB (2,5-dihydroxybenzoic acid) as matrices, and sodium trifluoroacetate as a cationizing agent. Measurements were performed in Reflector / Positive mode, with a mass range of m / z = 20 to 4000.

[0081] The first bismuth compound may be a mixture of multiple first phosphates and multiple other compounds bonded to bismuth. The first bismuth compound is preferably a mixture of a first phosphate having one (meth)acryloyl group and a first phosphate having two (meth)acryloyl groups bonded to bismuth. Such first bismuth compounds tend to be highly compatible with polymerizable compounds.

[0082] In such a first bismuth compound, the ratio of the first phosphate ester having two (meth)acryloyl groups to 1 mol of the first phosphate ester having one (meth)acryloyl group is preferably 0.05 to 3 mol, more preferably 0.10 to 2 mol, and even more preferably 0.15 to 1 mol.

[0083] Examples of suitable first bismuth compounds include compounds represented by the following formulae (III) to (V).

[0084]

[0085]

[0086] In formulae (III) to (V), R is each independently a hydrogen atom or a methyl group.

[0087] In the above formula (III), a+x+y+z=3. x represents the number of moles of 2-((meth)acryloyloxy)ethyl hydrogen phosphate residues. y represents the number of moles of 2-((meth)acryloyloxy)ethyl phenyl phosphate residues. z represents the number of moles of bis[2-((meth)acryloyloxy)ethyl]phosphate residues. a represents the number of moles of (meth)acrylic acid residues.

[0088] In the above formula (IV), 2b+u+v+w=3. u represents the number of moles of 2-((meth)acryloyloxy)ethyl hydrogen phosphate residues. v represents the number of moles of 2-((meth)acryloyloxy)ethyl phenyl phosphate residues. w represents the number of moles of bis[2-((meth)acryloyloxy)ethyl]phosphate residues. b represents the number of moles of salicylic acid residues.

[0089] In the above formula (V), 2c + q + r + 2s + t = 3. q represents the number of moles of 2-((meth)acryloyloxy)ethyl hydrogen phosphate residues. r represents the number of moles of 2-((meth)acryloyloxy)ethyl phenyl phosphate residues. s represents the number of moles of 2-((meth)acryloyloxy)ethyl phosphate residues. t represents the number of moles of bis[2-((meth)acryloyloxy)ethyl] phosphate residues. c represents the number of moles of salicylic acid residues.

[0090] It should be noted that each of the first bismuth compounds represented by formulae (III) to (V) may be a mixture of multiple compounds rather than a single compound. In this case, the molar number of each residue is assumed to represent the molar number of the entire mixture.

[0091] In the above formula (III), considering that the first bismuth compound can be produced at low temperatures and exhibits minimal coloration, when a = 0, x:y:z is preferably 1:0.05 to 3:0.5 to 30, more preferably 1:0.1 to 2:1 to 20, and even more preferably 1:0.15 to 1:1.5 to 10. Furthermore, from the perspective of further reducing coloration, a = 0 and y = 0 can also be used.

[0092] In the above formula (III), when a=other than 0, a:(x+y+z)=0.1 to 10:1 is preferred, a:(x+y+z)=0.1 to 5:1 is more preferred, and a:(x+y+z)=0.1 to 1:1 is even more preferred. In this case, x:y:z=1:0.05 to 3:0.5 to 30 is preferred, x:y:z=1:0.1 to 2:1 to 20 is more preferred, and x:y:z=1:0.15 to 1:1.5 to 10 is even more preferred.

[0093] In the above formula (IV), when b=0, it is the same as the above definition except that x is replaced by u, y is replaced by v, and z is replaced by w.

[0094] In the above formula (IV), when b=other than 0, preferably b:(u+v+w)=1:0.1-30, more preferably b:(u+v+w)=1:0.2-20, further preferably b:(u+v+w)=1:0.3-10, and particularly preferably b:(u+v+w)=1:0.5-5. In this case, preferably u:v:w=1:0.05-20:0.1-40, more preferably u:v:w=1:0.1-10:0.2-20, and further preferably u:v:w=1:0.2-5:0.4-10.

[0095] In the above formula (V), when c=0, preferably q:r:s:t=1:0.1-50:0.05-20:0.1-40, more preferably q:r:s:t=1:0.3-30:0.1-10:0.2-20, and further preferably q:r:s:t=1:0.5-20:0.2-5:0.4-10.

[0096] In the above formula (V), when c=other than 0, preferably c:(q+r+s+t)=1:0.1-30, more preferably c:(q+r+s+t)=1:0.2-20, further preferably c:(q+r+s+t)=1:0.3-10, and particularly preferably c:(q+r+s+t)=1:0.5-5. In this case, preferably q:r:s:t=1:0.1-50:0.05-20:0.1-40, more preferably q:r:s:t=1:0.3-30:0.1-10:0.2-20, and further preferably q:r:s:t=1:0.5-20:0.2-5:0.4-10.

[0097] The first bismuth compound is, for example, a phosphate or complex salt represented by the following formula (3).

[0098]

[0099] In the above formula (3), Q 1 , Q 2 , Q3 and a 3 Same as the above formula (2).

[0100] a 4 A number greater than 0 and less than 3.

[0101] a 5 A number greater than 0 and less than 3.

[0102] a 4 +a 5 is 3.

[0103] The first bismuth compound may be a composition containing compounds other than the first bismuth compound. This composition is hereinafter also referred to as the first bismuth composition. The first bismuth composition may also contain a phosphate compound produced as a by-product during production or unreacted raw materials.

[0104] Removing these by-produced phosphate compounds or unreacted raw materials from the first bismuth compound requires a lot of labor in industry. In addition, these by-produced phosphate compounds or unreacted raw materials can help improve the solubility in the radical polymerizable monomer.

[0105] Examples of by-produced phosphoric acid compounds include dimers of phosphoric acid esters having one (meth)acryloyl group (monophosphate), dimers of phosphoric acid esters having two (meth)acryloyl groups (diester), and esters of bismuth salicylate or bismuth (meth)acrylate with phosphoric acid.

[0106] Examples of the unreacted raw material include phosphoric acid esters having one (meth)acryloyl group (monophosphate), phosphoric acid esters having two (meth)acryloyl groups (diester), bismuth salicylate, and bismuth (meth)acrylate.

[0107] In the first bismuth composition, the proportion of compounds other than the first bismuth compound is, for example, 30% by mass or less. This proportion has no lower limit, and according to one example, it is 0% by mass, and according to another example, it is 5% by mass. This proportion can be determined by using 1 The by-produced phosphoric acid compound and unreacted raw material in the first bismuth composition were quantitatively confirmed by the internal standard method of H-NMR.

[0108] In addition, the first bismuth composition may also include a compound derived from bismuth oxide. The compound derived from bismuth oxide is, for example, a compound formed by bonding bismuth oxide to a phosphate ester, (meth) acrylic acid, and / or salicylic acid having a (meth) acryloyl group. Although the structure of the compound derived from bismuth oxide is unclear, it is believed that the hydroxyl group formed on the surface of the bismuth oxide is bonded to the carboxyl group of the phosphate ester, (meth) acrylic acid, or salicylic acid. It should be noted that the compound derived from bismuth oxide is very difficult to separate from the first bismuth compound. Therefore, when a compound derived from bismuth oxide is produced as a by-product, it is preferably used in a state containing a compound derived from bismuth oxide. When a compound derived from bismuth oxide is produced as a by-product, it is desirable to adjust the manufacturing conditions, etc. to make its amount within a range that does not reduce the solubility of the first bismuth composition. It should be noted that the compound derived from bismuth oxide can be comprehensively judged based on its manufacturing conditions, or methods such as IR, NMR, and XPS.

[0109] [Method for producing the first bismuth compound]

[0110] The method for producing the first bismuth compound is not particularly limited, but is preferably produced by reacting the second bismuth compound with the first phosphate ester. Specifically, the second bismuth compound is preferably produced by reacting the first phosphate ester with an aliphatic hydrocarbon solvent or an aromatic solvent, optionally with a polymerization inhibitor, to dehydrate the second bismuth compound.

[0111] The second bismuth compound is an organic compound containing bismuth. The second bismuth compound contains bismuth (meth)acrylate or bismuth subsalicylate. There are no particular limitations on the bismuth (meth)acrylate or bismuth subsalicylate, and commercially available products can be used.

[0112] Note that bismuth subsalicylate is a compound in which salicylic acid is bonded to bismuth, and is represented by the following formula (VI).

[0113]

[0114] The production method of bismuth subsalicylate is not particularly limited, and it can be produced by a known method.

[0115] A commercially available product can be used as the first phosphate ester. The first phosphate ester may be a phosphate ester having one (meth)acryloyl group, a phosphate ester having two (meth)acryloyl groups, or a mixture thereof.

[0116] Examples of the phosphoric acid ester having one (meth)acryloyl group include 2-(methacryloyloxy)ethyl dihydrogen phosphate and diphenyl 2-methacryloyloxyethyl phosphate.

[0117] Examples of the phosphoric acid ester having two (meth)acryloyl groups include bis[2-(methacryloyloxy)ethyl] hydrogen phosphate and phenyl[2-(methacryloyloxy)ethyl] hydrogen phosphate.

[0118] In order to improve compatibility, it is preferred to add a phosphate triester such as diphenyl 2-methacryloyloxyethyl phosphate, phenyl bis[2-(methacryloyloxyethyl)]phosphate, or tris[2-(methacryloyloxyethyl)]phosphate as the first phosphate. Using a phosphate triester having a phenyl group allows for the successful introduction of the monovalent phenyl phosphate diester having one (meth)acryloyl group in formulas (III) to (V).

[0119] The amount of the triester phosphate used is preferably 0.1 to 20 mol, more preferably 0.2 to 5 mol, per 1 mol of the total of the phosphate ester having one (meth)acryloyl group and the phosphate ester having two (meth)acryloyl groups.

[0120] The amount of the first phosphate used may be determined so as to obtain the desired first bismuth compound. Specifically, the amount of the first phosphate used is preferably within a range of 0.3 to 10 mol per mol of the second bismuth compound.

[0121] (Aliphatic hydrocarbon solvent or aromatic solvent)

[0122] In this embodiment, the second bismuth compound and the first phosphate are preferably stirred and mixed in an aliphatic hydrocarbon solvent or an aromatic solvent to conduct the reaction. Water is generated in the reaction system during this process, and therefore the generated water is preferably dehydrated. To facilitate dehydration of the generated water, an aliphatic hydrocarbon solvent or an aromatic solvent with a high boiling point, specifically a boiling point of 100°C or higher, is preferably used. Alternatively, an aliphatic hydrocarbon solvent and an aromatic solvent may be mixed to form a mixed solution for use.

[0123] Examples of the aliphatic hydrocarbon solvent or aromatic solvent include hexane, heptane, nonane, decane, undecane, dodecane, xylene, dimethoxybenzene and isomers thereof; benzene, toluene, chlorobenzene, bromobenzene, anisole; petroleum ether, petroleum benzine, benzoin, and the like.

[0124] The amount of the aliphatic hydrocarbon solvent or aromatic solvent used is not particularly limited as long as it is an amount sufficient to mix the second bismuth compound and the first phosphate ester. Taking into account the productivity of the first bismuth compound, the aliphatic hydrocarbon solvent or aromatic solvent is preferably used in a ratio of 5 to 100 mL per 1 g of the second bismuth compound.

[0125] (Reaction Conditions)

[0126] The method for introducing the second bismuth compound and the first phosphate into the reaction system is not particularly limited. For example, the following method can be used: the second bismuth compound diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed, and the first phosphate diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed are added together into the reaction system and stirred and mixed. In addition, the following method can be used: an aliphatic hydrocarbon solvent or an aromatic solvent is introduced into the reaction system in advance, and then the second bismuth compound diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed, and the first phosphate diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed are added together thereto and stirred and mixed. In addition, the following means can be used: one of the components is introduced into the reaction system in advance, and then the other component is introduced into the reaction system and stirred and mixed. Among them, in order to reduce the coloration of the obtained first bismuth compound and improve productivity, the following method is preferably used. First, the second bismuth compound is dispersed in an aliphatic hydrocarbon solvent or an aromatic solvent. At this time, the second bismuth compound sometimes does not dissolve. In this case, it is preferred to use an ultrasonic device or the like to crush the lumps of the second bismuth compound in a manner such that no lumps of the second bismuth compound exist. Then, the first phosphate ester is added to the turbid solution in which the second bismuth compound is dispersed, and stirring and heating are started.

[0127] The temperature (reaction temperature) during stirring of the components may be the reflux temperature of the aliphatic hydrocarbon solvent or the aromatic solvent. To further reduce the coloration of the obtained first bismuth compound, it is desirable to carry out the stirring at the following temperature: preferably an oil bath temperature of 30 to 150°C, more preferably a temperature of 40 to 140°C, and even more preferably a temperature of 45 to 120°C.

[0128] Furthermore, when the reaction temperature is 30-110°C, the reaction system is preferably placed under reduced pressure to remove (dehydrate) the water generated within the reaction system. In this case, the second bismuth compound and the first phosphate can be mixed while dehydrating, or the two can be mixed before dehydration. However, considering the efficiency of the reaction, it is preferred to dehydrate the two compounds while they are mixed.

[0129] The reaction time is not particularly limited, but is usually 1 hour to 6 hours.

[0130] In consideration of operability, the reaction may be carried out in any of an air atmosphere, an inert gas atmosphere, and a dry air atmosphere. However, in consideration of operability, the reaction is preferably carried out in an air atmosphere.

[0131] After the reaction under the above conditions, if the first bismuth compound obtained contains insoluble turbid components after distillation and concentration by removing the solvent, it is desirable to separate these components by filtration or centrifugation. Furthermore, a solvent that is soluble in the reaction solvent used and does not dissolve the first bismuth compound is added to the concentrated reaction solution obtained by this treatment to reprecipitate and purify the solution. If a high-boiling-point solvent remains, the above decantation operation is repeated to replace the solvent. The remaining solvent is then distilled off and vacuum dried to extract the first bismuth compound.

[0132] In the composition of this embodiment, the content of the first bismuth compound is, for example, 80.0% by mass or more and 99.8% by mass or less. If the content of the first bismuth compound is relatively high, when the composition is used to prepare a curable composition, the radiation shielding capability of the cured product tends to be improved. The content of the first bismuth compound is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. On the other hand, if the content of the first bismuth compound is too high, the odor of the cured product may become stronger. The content of the first bismuth compound is preferably 99.5% by mass or less.

[0133] <Coordinating organic compounds>

[0134] A coordinating organic compound is an organic compound that can coordinate to bismuth. The present inventors have studied the use of the acid dissociation constant pKa as an indicator of the coordination, and found that the pKa of a suitable coordinating organic compound is 1.5 or greater. The acid dissociation constant pKa refers to the acid dissociation constant in water. For example, experimentally, the acid dissociation constant pKa can be calculated by titration and assuming the conditions of the state. Specifically, the calculation results obtained by using ACD / Lab software V11.02 recorded in SciFinder-n were used. The value assumed in water was used as a unified physical property index for each compound.

[0135] The acid dissociation constant pKa of the coordinating organic compound is preferably 2.0 or greater and 15.0 or less. If a coordinating organic compound having an acid dissociation constant pKa within this range is used, when the composition of this embodiment is used to prepare a curable composition, there is a tendency to obtain a cured product with low yellowness. The acid dissociation constant pKa of the coordinating organic compound may be 3 or greater, 4 or greater, or 6 or greater. The acid dissociation constant pKa of the coordinating organic compound may be 14 or less, 11 or less, or 10 or less.

[0136] The molecular weight (relative molecular mass) of the coordinating organic compound is preferably 17 to 400. It is believed that a coordinating organic compound with a molecular weight within this range is more likely to coordinate with bismuth. The molecular weight of the coordinating organic compound is more preferably 18 to 300, and even more preferably 28 to 200.

[0137] The boiling point of the coordinating organic compound at 1 atmosphere is preferably 20°C to 500°C. Using a coordinating organic compound with a boiling point within this range tends to further reduce the odor of the cured product when the composition of this embodiment is used to prepare a curable composition. The boiling point of the coordinating organic compound is more preferably 30°C to 400°C, and even more preferably 120°C to 360°C.

[0138] In the composition of this embodiment, the ratio M1 / M2 of the mass M1 of the first bismuth compound to the mass M2 of the coordinating organic compound is preferably 4 or more and 4990 or less. A higher ratio M1 / M2 tends to improve the radiation shielding capability of a cured product when the composition of this embodiment is used to prepare a curable composition. A lower ratio M1 / M2 tends to reduce the odor of the cured product. The ratio M1 / M2 is more preferably 15 or more and 300 or less, and even more preferably 20 or more and 100 or less. The ratio M1 / M2 may also be 10 or more and 700 or less.

[0139] In the composition of the present embodiment, if the proportion of the coordinating organic compound is high, when the composition is used to prepare a curable composition, there is a tendency to reduce the odor of the cured product. The proportion of the coordinating organic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. On the other hand, if the proportion of the coordinating organic compound is too high, when the composition of the present embodiment is used to prepare a curable composition, the radiation shielding ability of the cured product may decrease. The proportion of the coordinating organic compound is preferably 8% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less.

[0140] The coordinating organic compound includes, for example, at least one, preferably two or more compounds selected from the group consisting of: a compound having an imidazole skeleton, a compound having a pyrazole skeleton, a compound having a triazole skeleton, a compound having a tetrazole skeleton, a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom and an unsaturated bond, an unsaturated dicarboxylic acid, an unsaturated carboxylic ester and an unsaturated carboxylic anhydride.

[0141] The coordinating organic compound preferably contains at least one selected from the group consisting of a compound having an imidazole skeleton, a compound having a pyrazole skeleton, a compound having a triazole skeleton, and a compound having a tetrazole skeleton.

[0142] The compound having an imidazole skeleton has a skeleton represented by the following formula (a).

[0143]

[0144] Examples of the compound having an imidazole skeleton include imidazole, 1-vinylimidazole, 1-allylimidazole, N-acetylimidazole, benzimidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-cyanomethylimidazole, 1-(3-aminopropyl)imidazole, 2-methylimidazole, 2-methyl-1-vinylimidazole, 2-hydroxymethyl-1-methylimidazole, 4-hydroxymethyl-5-methyl ... 1-formylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-chloroimidazole, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole, 4-fluoroimidazole, 2-formylimidazole, 2-ethyl-4-imidazole, 4-formylimidazole, 4-ethylimidazole, 4-cyanomethylimidazole, 2-imidazolecarboxylic acid, 4-imidazolecarboxylic acid, 1-isopropylimidazole, 2-isopropylimidazole, 1,2-dimethylimidazole, etc. The compound having an imidazole skeleton preferably contains at least one compound selected from the group consisting of imidazole, 1-vinylimidazole, 1-allylimidazole, 2-methylimidazole, N-acetylimidazole, trimethylsilylimidazole and 1,2-dimethylimidazole, and more preferably contains imidazole.

[0145] The compound having a pyrazole skeleton has a skeleton represented by the following formula (b).

[0146]

[0147] Examples of the compound having a pyrazole skeleton include pyrazole, 1-methylpyrazole, 1-ethylpyrazole, 1-isopropylpyrazole, 1-nitropyrazole, 3-methylpyrazole, 3-aminopyrazole, 3-nitropyrazole, 4-methylpyrazole, 4-aminopyrazole, 4-chloropyrazole, 4-nitropyrazole, 3-amino-1-methylpyrazole, 3-amino-5-methylpyrazole, 3-amino-5-hydroxypyrazole, 5-amino-1-methylpyrazole, 5-hydroxy-1 -methylpyrazole, 1,2-dihydropyrazol-3-one, 3-formylpyrazole, 1,3-dimethylpyrazole, 1,5-dimethylpyrazole, 3,5-dimethylpyrazole, 3-amino-4-cyanopyrazole, 4-formyl-1-methylpyrazole, 1,3,5-trimethylpyrazole, 5-amino-1,3-dimethylpyrazole, 5-amino-1-ethylpyrazole, pyrazole-4-carboxylic acid, pyrazole-3-carboxylic acid, 5-(hydroxymethyl)-1-methylpyrazole, etc. The compound having a pyrazole skeleton preferably contains pyrazole.

[0148] The compound having a triazole skeleton includes a compound having a 1,2,3-triazole skeleton and a compound having a 1,2,4-triazole skeleton.

[0149] The compound having a 1,2,3-triazole skeleton has a skeleton represented by the following formula (c).

[0150]

[0151] Examples of the compound having a 1,2,3-triazole skeleton include 1,2,3-triazole, 1H-benzotriazole, and 2H-benzotriazole. The compound having a 1,2,3-triazole skeleton preferably contains 1,2,3-triazole.

[0152] The compound having a 1,2,4-triazole skeleton has a skeleton represented by the following formula (d).

[0153]

[0154] Examples of the compound having a 1,2,4-triazole skeleton include 1,2,4-triazole, 3-methyl-1H-1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 1-hydroxymethyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3,5-amino-1,2,4-triazole, and methyl 1,2,4-triazole-3-carboxylate. The compound having a 1,2,4-triazole skeleton preferably includes 1,2,4-triazole.

[0155] The compound having a tetrazole skeleton has a skeleton represented by the following formula (e).

[0156]

[0157] Examples of the compound having a tetrazole skeleton include tetrazole, 1-methyl-1H-tetrazole, 5-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, and 5-(2-pyridyl)-1H-tetrazole. The compound having a tetrazole skeleton preferably contains tetrazole.

[0158] The coordinating organic compound includes, for example, a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom and an unsaturated bond. The number of heteroatoms is, for example, 1 or more and 5 or less, preferably 1 or 2. As such a compound, in addition to the above-mentioned compound having an imidazole skeleton, there are also exemplified: allyl isonicotinate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, indole, carbazole, 1,2-benzisothiazol-3(2H)-one, piperonal, allyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, 2-(tert-butylamino)ethyl methacrylate, and the like.

[0159] The coordinating organic compound includes, for example, unsaturated dicarboxylic acids. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentaconedioic acid, methylene succinic acid, allylmalonic acid, propylidene succinic acid, 2,4-hexadienedioic acid, and acetylenedicarboxylic acid. The unsaturated dicarboxylic acid preferably includes maleic acid.

[0160] The coordinating organic compound includes, for example, an unsaturated carboxylic acid ester. Examples of the unsaturated carboxylic acid ester include 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, and diallyl maleate. The unsaturated carboxylic acid ester preferably includes at least one compound selected from the group consisting of 2-dimethylaminoethyl acrylate and 2-dimethylaminoethyl methacrylate.

[0161] The coordinating organic compound includes, for example, unsaturated carboxylic acid anhydrides. Examples of the unsaturated carboxylic acid anhydrides include acrylic anhydride, methacrylic anhydride, and maleic anhydride.

[0162] Preferred specific examples of the coordinating organic compound include imidazole, 1-vinylimidazole, 1-allylimidazole, N-acetylimidazole, trimethylsilylimidazole, pyrazole, triazole, 1H-tetrazole, 1,2,3-benzotriazole, benzimidazole, allyl isonicotinate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, indole, carbazole, 2-methylimidazole, 4-methylimidazole, At least one compound selected from the group consisting of oxazole, 1,2-benzisothiazol-3(2H)-one, 2-isopropylimidazole, 1,2-dimethylimidazole, levomenthol, piperonal, triallyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, 2-(tert-butylamino)ethyl methacrylate, 4-acryloylmorpholine, triacryloylhexahydrotriazine, dimethylpyrazole, linalool, camphor, acrylic acid, methacrylic acid, maleic acid, acrylic anhydride, methacrylic anhydride, and maleic anhydride.

[0163] The coordinating organic compound preferably includes at least one compound selected from the group consisting of imidazole, 2-methylimidazole, 1-vinylimidazole, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, triallylamine, and maleic anhydride.

[0164] It should be noted that carboxylic acid anhydride can be used as a carboxylic acid precursor. The acid dissociation constant pKa is the value of the corresponding carboxylic acid.

[0165] The coordinating organic compound preferably includes a first coordinating organic compound and a second coordinating organic compound of a different type from the first coordinating organic compound. If a plurality of coordinating organic compounds are included, the odor can be further reduced due to the synergistic effect of the coordinating organic compounds.

[0166] The coordinating organic compound preferably comprises a compound having a pyrazole skeleton, a compound having a triazole skeleton, a compound having a tetrazole skeleton, a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom and an unsaturated bond, an unsaturated dicarboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid anhydride, and comprises a compound having an imidazole skeleton. If a compound having an imidazole skeleton is included, when the composition of the present embodiment is used to prepare a curable composition, the viscosity of the curable composition tends to decrease and the handleability tends to improve.

[0167] In the case of a plurality of coordinating organic compounds, the proportion of the compound having an imidazole skeleton is preferably 10% by mass or more, more preferably 25% by mass or more, and further preferably 40% by mass or more. According to one example, the proportion of the compound having an imidazole skeleton is 90% by mass or less, and according to another example, 60% by mass or less.

[0168] The coordinating organic compound preferably comprises at least one compound selected from the group consisting of a compound having an imidazole skeleton, a compound having a pyrazole skeleton, a compound having a triazole skeleton, a compound having a tetrazole skeleton, a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom and an unsaturated bond, and an unsaturated dicarboxylic acid and an unsaturated carboxylic acid ester, and further comprises an unsaturated carboxylic acid anhydride. If an unsaturated carboxylic acid anhydride is included, the water absorption tends to be enhanced.

[0169] In the plurality of coordinating organic compounds, the proportion of the unsaturated carboxylic acid anhydride is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. According to one example, the proportion of the unsaturated carboxylic acid anhydride is 90% by mass or less, and according to another example, it is 60% by mass or less.

[0170] The coordinating organic compound preferably contains both a compound having an imidazole skeleton and an unsaturated carboxylic acid anhydride. The coordinating organic compound may contain only a compound having an imidazole skeleton and an unsaturated carboxylic acid anhydride, or may contain other compounds.

[0171] <Method for preparing the composition>

[0172] The composition of this embodiment can be prepared, for example, by mixing the first bismuth compound and the coordinating organic compound.

[0173] Curable composition

[0174] The curable composition of this embodiment comprises the composition of this embodiment described above and a first polymerizable compound. Specifically, the curable composition of this embodiment comprises a first bismuth compound, a coordinating organic compound, and a first polymerizable compound. The first polymerizable compound has at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

[0175] In the curable composition of this embodiment, the content of the first bismuth compound is, for example, 20% by mass or more and 90% by mass or less. A higher content of the first bismuth compound tends to improve the radiation shielding effect of the cured product. The content of the first bismuth compound is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. On the other hand, if the content of the first bismuth compound is too high, the odor of the cured product may become stronger. The content of the first bismuth compound is preferably 80% by mass or less.

[0176] In the curable composition of this embodiment, if the proportion of the coordinating organic compound is high, there is a tendency to reduce the odor of the cured product. The proportion of the coordinating organic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. On the other hand, if the proportion of the coordinating organic compound is too high, the radiation shielding ability of the cured product may decrease. The proportion of the coordinating organic compound in the curable composition is preferably 8% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less. For example, it can be used 1 The ratio was determined by H-NMR.

[0177] In the curable composition of the present embodiment, the total content of the first bismuth compound and the coordinating organic compound is preferably 10% by mass or more and 90% by mass or less.

[0178] <First polymerizable compound>

[0179] The first polymerizable compound has at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

[0180] The boiling point of the first polymerizable compound at 1 atmosphere is preferably 90°C or higher. If a first polymerizable compound with a higher boiling point is used, the odor of the cured product tends to be reduced. The boiling point of the first polymerizable compound is preferably 100°C or higher, more preferably 140°C or higher. There is no particular upper limit to the boiling point of the first polymerizable compound. According to one example, it is 200°C or lower, and according to another example, it is 300°C or lower. For example, the boiling point of the first polymerizable compound can be measured by thermogravimetric (TG) analysis. During the TG measurement, a differential thermal gravimetric measurement device (manufactured by Rigaku Corporation, TG8120) is used to scan from room temperature to 500°C under air flow at a heating rate of 10°C / min.

[0181] The content of the first polymerizable compound in the curable composition of this embodiment is, for example, 10% by mass or more and 80% by mass or less. 1 The content was measured by H-NMR.

[0182] The first polymerizable compound preferably comprises a monofunctional radically polymerizable compound having one radically polymerizable site per molecule. If the curable composition contains a monofunctional radically polymerizable compound, the compatibility of the first bismuth compound tends to improve. The monofunctional radically polymerizable compound preferably has a boiling point of 150°C or higher, more preferably 180°C or higher, at 1 atmosphere.

[0183] Examples of the first polymerizable compound having an acryloyl group include the following commercially available monofunctional free radical polymerizable compounds: acrylic acid, acrylamide, phenyl acrylate, benzyl acrylate, isobutyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, isocyanatoethyl acrylate, and acryloyloxymethyltrimethoxysilane.

[0184] Examples of the first polymerizable compound having a methacryloyl group include various commercially available monofunctional radical polymerizable compounds such as methacrylic acid, methacrylamide, phenyl methacrylate, benzyl methacrylate, isobutyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, and methacryloxymethyltrimethoxysilane.

[0185] Examples of the first polymerizable compound having a vinyl group include the following commercially available monofunctional radical polymerizable monomers: vinylpyridine, vinylpyrrolidone, methylstyrene and its structural isomers, methoxystyrene and its structural isomers, methylstyrene dimer, chlorostyrene, bromostyrene, divinylbenzene, and the like.

[0186] Examples of the first polymerizable compound having an allyl group include various commercially available monofunctional radical polymerizable monomers such as allyl methyl carbonate, allyl phenyl ether, 4-allyloxytoluene, allyloxytrimethylsilane, allyl benzoate, allyl methacrylate, and allyl glycidyl ether.

[0187] Among them, from the viewpoint of optical properties and impact resistance after curing, suitable monofunctional radical polymerizable compounds include (meth)acrylates represented by the following formula (I).

[0188]

[0189] In the above formula (I), R 1 It is a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms and 1 to 3 heteroatoms, an aryl group having 4 to 10 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms and 1 to 3 heteroatoms.

[0190] R 1 Preferred is a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or a heterocycloalkyl group having 3 to 10 carbon atoms and 1 to 3 heteroatoms. More preferred is a linear or branched alkoxy group having 1 to 10 carbon atoms, or a heterocycloalkyl group having 3 to 10 carbon atoms and 1 to 3 heteroatoms. Further preferred is a methoxy group or a tetrahydrofuranyl group.

[0191] R 2 It is a linear or branched alkylene group having 1 to 10 carbon atoms or an alkylene oxide group having 1 to 10 carbon atoms.

[0192] R 2 It is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and more preferably a methylene group or an ethylene group.

[0193] R 3 is a hydrogen atom or a methyl group.

[0194] a is 0 or 1. Preferably, a is 1.

[0195] Specific examples of the (meth)acrylate represented by formula (I) include at least one selected from the group consisting of methoxyethyl acrylate (MEMA), ethoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, tetrahydrofurfuryl acrylate (THFAA), and tetrahydrofurfuryl methacrylate (THFMA).

[0196] In the curable composition of this embodiment, the content of the monofunctional free radical polymerizable compound is preferably 10% by mass or more and 80% by mass or less. A higher content of the monofunctional free radical polymerizable compound tends to improve the compatibility of the first bismuth compound. A lower content of the monofunctional free radical polymerizable compound tends to reduce the odor of the cured product and improve its impact resistance. More preferably, the content of the monofunctional free radical polymerizable compound is 10% by mass or more and 30% by mass or less. This content can be measured, for example, by NMR.

[0197] The curable composition of the present embodiment preferably includes a plurality of monofunctional free radical polymerizable compounds. If a plurality of monofunctional free radical polymerizable compounds are included, there is a tendency for the compatibility of the first bismuth compound to be improved. The curable composition of the present embodiment may include a monofunctional free radical polymerizable compound having a (meth) acryloyl group and a monofunctional free radical polymerizable compound having a vinyl group. The ratio M4 / M5 of the mass M4 of the monofunctional free radical polymerizable compound having a (meth) acryloyl group to the mass M5 of the monofunctional free radical polymerizable compound having a vinyl group is, for example, 0.1 or more and 10 or less, preferably 1 or more and 5 or less.

[0198] The curable composition of this embodiment preferably contains two or more (meth)acrylates represented by the above formula (I), and more preferably contains R 1 (Meth)acrylates of tetrahydrofuranyl and R in the above formula (I) 1 At least one of the (meth)acrylates containing methoxy groups. 1 If the (meth)acrylate is a tetrahydrofuranyl group, the compatibility of the first bismuth compound tends to be improved. 1 In particular, it is more preferable to include R 1 R is a methoxy (meth)acrylate. 1 The mass of methoxy (meth)acrylate M6 and R 1 The ratio M6 / M7 of the mass M7 of the tetrahydrofuranyl (meth)acrylate is preferably 0.1 to 10. Within this range, the compatibility of the first bismuth compound in the curable composition is improved, and the hardness of the cured product is enhanced. The ratio M6 / M7 is more preferably 0.3 to 5, and even more preferably 0.5 to 3.

[0199] The ratio (M1 / M10) of the mass M1 of the first bismuth compound to the mass M10 of the monofunctional radically polymerizable compound is preferably 0.25 or greater and 100 or less. A higher ratio tends to improve the radiation shielding capability of the cured product. A lower ratio tends to improve the compatibility of the first bismuth compound. More preferably, the ratio is 1 or greater and 6 or less.

[0200] The first polymerizable compound preferably includes a polyfunctional free radical polymerizable compound having multiple free radical polymerizable sites per molecule. Including a polyfunctional free radical polymerizable compound can further improve the mechanical properties, such as impact resistance, of the cured product of the curable composition. Commercially available polyfunctional free radical polymerizable compounds can be used without limitation. The boiling point of the polyfunctional free radical polymerizable compound at 1 atmosphere is preferably 100°C or higher, more preferably 140°C or higher.

[0201] In consideration of solubility, viscosity of the composition, and impact resistance of the cured product, a di(meth)acrylate represented by the following formula (II) is preferably used as the polyfunctional radical polymerizable compound.

[0202]

[0203] In the above formula (II), R 4 It is a linear or branched alkylene group having 1 to 10 carbon atoms, or a linear or branched alkyleneoxy group having 1 to 10 carbon atoms.

[0204] R 4 It is preferably a linear or branched alkyleneoxy group having 1 to 10 carbon atoms, and more preferably an ethyleneoxy group.

[0205] R 5 and R 6 are each independently a hydrogen atom or a methyl group.

[0206] n is 1 or more and 50 or less. n is preferably a number of 3 or more and 30 or less.

[0207] Specific examples of the di(meth)acrylate represented by formula (II) include bifunctional (meth)acrylates selected from the group consisting of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, polytetramethylene glycol dimethacrylate, and polytetramethylene glycol diacrylate.

[0208] In the curable composition of this embodiment, the proportion of the multifunctional free radical polymerizable compound is preferably 0% by mass or more and 50% by mass or less. If this proportion is high, there is a tendency for the impact resistance of the cured product to be improved. If this proportion is low, there is a tendency for the compatibility of the first bismuth compound to be improved. This proportion is more preferably 5% by mass or more and 20% by mass or less. For example, this proportion can be measured using NMR. The measurement conditions of NMR are the same as those described above.

[0209] The ratio (M1 / M3) of the mass M1 of the first bismuth compound to the mass M3 of the polyfunctional radically polymerizable compound is preferably 0 or greater and 100 or less. A higher ratio tends to improve the radiation shielding capability of the cured product. A lower ratio tends to improve the impact resistance of the cured product. More preferably, the ratio is 1 or greater and 10 or less.

[0210] The curable composition of this embodiment preferably contains both a monofunctional free radical polymerizable compound and a polyfunctional free radical polymerizable composition. The ratio M10 / M3 of the mass M10 of the monofunctional free radical polymerizable compound to the mass M3 of the polyfunctional free radical polymerizable compound is preferably 0.1 or more and 300 or less. If this ratio is high, the compatibility of the first bismuth compound tends to be improved. If this ratio is low, the impact resistance of the cured product tends to be improved. More preferably, this ratio is 0.1 or more and 10 or less.

[0211] The curable composition of this embodiment preferably contains R 1 is a tetrahydrofuranyl (meth)acrylate, R in the above formula (I) 1 (Meth)acrylates containing methoxy groups and di(meth)acrylates represented by the above formula (II). By including these three polymerizable compounds, a cured product with reduced odor and better impact resistance can be obtained. 1 The mass M6 and R of methoxy (meth)acrylate 1 The ratio M8 / M9 of the total mass M8 of the mass M7 of the (meth)acrylate having a tetrahydrofuryl group to the mass M9 of the di(meth)acrylate represented by the above formula (II) is preferably 0.1 to 10, more preferably 0.3 to 5, and even more preferably 0.5 to 3.

[0212] The curable composition of the present embodiment may contain 10% by mass or less of a nitrile compound. The content of the nitrile compound in the curable composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. If the content of the nitrile compound is small, there is a tendency for the odor of the cured product to decrease. The lower limit of the content of the nitrile compound is, according to one example, 100 ppm by mass or more, and according to another example, 0% by mass. For example, it is possible to utilize 1The ratio is measured by H-NMR. The measurement conditions of NMR are the same as those described above.

[0213] Examples of the nitrile compound include acrylonitrile, methacrylonitrile, crotononitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, allyl cyanide, allyl cyanoacetate, fumaronitrile, and 5-norbornene-2-carbonitrile.

[0214] The curable composition of this embodiment may contain a second polymerizable compound. The second polymerizable compound refers to a polymerizable compound having a boiling point of less than 90°C at 1 atmosphere. The content of the second polymerizable compound in the curable composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. If the content of the second polymerizable compound is small, the odor of the cured product tends to decrease. The lower limit of the content of the second polymerizable compound is, according to one example, 1% by mass or more, and according to another example, 0% by mass. For example, it is possible to utilize 1 The ratio was determined by H-NMR.

[0215] Examples of the second polymerizable compound include methyl acrylate, allyl methyl ether, and allyl ethyl ether.

[0216] In the curable composition of the present embodiment, the content of the other radical polymerizable monomer is preferably 0 to 500 parts by mass, more preferably 0 to 400 parts by mass, and even more preferably 0 to 300 parts by mass per 100 parts by mass of the first bismuth compound.

[0217] Taking into account the radiation shielding effect, dispersibility, coloration reduction effect, etc., the ratio of the total amount of the polymerizable compound (hereinafter also referred to as the "total amount of the polymerizable compound") in the curable composition of this embodiment to the amount of the first bismuth compound is preferably set to 1 to 500 parts by mass, more preferably 5 to 300 parts by mass, and even more preferably 10 to 200 parts by mass relative to 100 parts by mass of the first bismuth compound.

[0218] When the curable composition of this embodiment is used as an antibacterial / antiviral material, the total amount of the polymerizable compound is preferably 1 to 20,000 parts by mass, more preferably 25 to 15,000 parts by mass, and even more preferably 10 to 9,900 parts by mass, relative to 100 parts by mass of the first bismuth compound, in consideration of its effect.

[0219] <Other compounding agents>

[0220] The curable composition of this embodiment may contain, in addition to the first bismuth compound, the coordinating organic compound, and the polymerizable compound, known additives generally incorporated into radically polymerizable curable compositions. Examples of such additives include radical polymerization initiators, antioxidants, release agents for improving mold release properties, pigments for adjusting the color tone of the cured product, and chain transfer agents for controlling polymerizability.

[0221] The content of each compounding agent may be within a range that does not inhibit the effects of the present invention. Specifically, the content of each compounding agent is preferably 0 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, and even more preferably 0.02 to 15 parts by mass, per 100 parts by mass of the total of the first bismuth compound, the coordinating organic compound, and the polymerizable compound.

[0222] <Method for preparing curable composition>

[0223] For example, the curable composition of the present embodiment can be prepared by mixing the first bismuth compound, the coordinating organic compound, the polymerizable compound, and various compounding agents as needed.

[0224] "Solid Object"

[0225] The cured product of the present embodiment is formed by curing the curable composition of the present embodiment. As the manufacturing method of the cured product, a known method can be adopted. Specifically, photopolymerization, thermal polymerization, or these two polymerization methods can be adopted. The appropriate polymerization method is determined by the free radical polymerization initiator mixed as needed.

[0226] <Physical properties of cured product>

[0227] The cured product of this embodiment contains a high concentration of bismuth, exhibits high transmittance, and exhibits minimal coloration. Bismuth has a high shielding ability against radiation such as X-rays. For example, the cured product, with a thickness of 2 mm, has a transmittance of 80% or greater at a wavelength of 560 nm, equivalent to X-ray shielding capability of lead foil with a thickness of 0.02 mm or greater, and a yellowness index of 40 or less.

[0228] Furthermore, when the total mass of the cured product is 100 mass %, the content of bismuth contained in the cured product can be 5 to 40 mass %.

[0229] The cured product of this embodiment may be a resin composition comprising bismuth and a (meth) acrylic resin. In the resin composition, when the polymerization inhibitor contained in the first bismuth compound in the manufacture is used as a reference for quantification, the phenol content based on the gas chromatography mass spectrometry (GC / MS) method may be 10 ppm or less. That is, the resin composition is a cured product of a curable composition comprising a coordinating organic compound, and therefore can reduce the phenol content that may be the cause of the odor. When the polymerization inhibitor contained in the first bismuth compound in the manufacture is used as a reference for quantification, the phenol content is preferably 5 ppm or less, more preferably below the detection limit. It should be noted that when the phenol content is calculated by the GC / MS method, the phenol content is calculated using the phenol content. 1 The same sample was measured by H NMR for quantification, and the area ratio of the two signals in the chromatogram was used as a reference.

[0230] Gas chromatography-mass spectrometry analysis was performed using a headspace GC / MS. Approximately 1 g of a resin sample was pulverized and placed in a vial. The sample was heated at 120° C. for 30 minutes, and the volatilized vapor was introduced into the GC for MS measurement.

[0231] <Applications of Cured Products>

[0232] The cured product of this embodiment is lightly colored and transparent, and therefore can be used as an optical article. Furthermore, despite being visible light transmissive, it has radiation shielding capability and can be used as a transparent radiation shielding material.

[0233] The optical article including the cured product of this embodiment can be used as a radiation shielding window material or a radiation shielding lens.

[0234] Furthermore, lenses including the cured product of this embodiment can be used as radiation shielding glasses.

[0235] Furthermore, the cured product of the present embodiment has antibacterial and antiviral properties and can therefore be used in applications requiring high sanitation.

[0236] Example

[0237] Hereinafter, the present invention will be described in detail using Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0238] <Analysis Method of First Bismuth Compound>

[0239] A Fourier transform infrared spectrometer (Spectrum One, manufactured by PerkinElmer) was used for IR measurement, and the measurement was performed by the ATR method using a single reflection and four accumulations.

[0240] A differential thermal and thermogravimetric analyzer (TG8120 manufactured by Rigaku Corporation) was used for TG-DTA measurement, and scanning was performed from room temperature to 500° C. at a temperature increase rate of 10° C. / min under air flow.

[0241] Raman scattering was measured using a Raman microscope (NRS-7100, manufactured by JASCO Corporation). 532 nm laser, 100x objective lens, 600 lines / mm grating, The aperture was set to 100 nm and the exposure time was 20 seconds × 2 for measurement.

[0242] 1 H-、 31 A nuclear magnetic resonance apparatus (JNM-ECA400II (trade name) manufactured by JEOL Ltd.) was used for the P-NMR measurement. Deuterated acetone was used as a solvent, and the measurement was performed at a sample concentration of 1% by mass.

[0243] The XPS measurement was performed using an X-ray photoelectron spectrometer (ESCA5701ci / MC manufactured by ULVAC-PHI, INCORPORATED). A monochromated Al-Kα (14 kV-330 W) X-ray source was used, and the aperture diameter was set to The photoelectron emission angle was set to 45 degrees. The sample was pulverized in an agate mortar, and the resulting powder was fixed on a substrate with carbon tape. The powder was then introduced into a chamber and measured.

[0244] MALDI-TOF-MS measurements were performed using a Bruker rapiflex TOF / TOF. CHCA (α-cyano-4-hydroxycinnamic acid), DIT (Dithranol), and DHB (2,5-dihydroxybenzoic acid) were used as matrices, and sodium trifluoroacetate was used as a cationizing agent. Measurements were performed in Reflector / Positive mode, with a mass range of m / z = 20 to 4000.

[0245] <Production Example 1: Production of a Composition Containing Bismuth Bound to Phosphate Ester (First Bismuth Compound)>

[0246] A 1000-mL eggplant-shaped flask was charged with 94.27 g of bismuth (III) subsalicylate (manufactured by Sigma-Aldrich, 260.35 mmol in terms of bismuth), 33.06 g of a mixture of bis[(2-methacryloyloxyethyl)] phosphate as a phosphoric diester and (2-methacryloyloxyethyl) phosphate as a phosphoric monoester (manufactured by Daihachi Chemical Industry Co., Ltd., MR-200, 162.04 mmol in terms of phosphoric acid value), 33.09 g of diphenyl 2-methacryloyloxyethyl phosphate as a phosphoric triester (manufactured by Daihachi Chemical Industry Co., Ltd., MR-260, 91.33 mmol), and 6.17 g of butylated hydroxytoluene (BHT, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) as a polymerization inhibitor, and 750 mL of toluene was added. The mixture was dispersed by ultrasonic waves using a bath-type sonicator to prepare a turbid solution.

[0247] The resulting turbid solution was transferred to a 1000 mL four-necked flask equipped with a Dean-Stark trap. The reaction was continued while stirring and heating at 130°C in an oil bath. The generated water was removed from the system. The point at which no more water was generated was considered the end point of the reaction. A pale yellow scattering solution with a slight amount of pale yellow precipitate was obtained.

[0248] The solution was concentrated to 250 mL using a vacuum evaporator. 8 g of alumina powder was added, and after standing overnight, suction filtration was performed using 5B filter paper. 3 g of activated carbon (Darco G60, manufactured by Norit) was added to the obtained light yellow suspension filtrate, and the mixture was centrifuged at 23830 × g for 8 hours. The supernatant from the centrifuge was pressure filtered using a membrane filter with a pore size of 0.2 μm to obtain a light yellow transparent filtrate. After the solvent was distilled off from the solution using a vacuum evaporator, the solution was redissolved in 250 mL of acetone. 3 g of activated carbon (Norit SX-Plus, manufactured by Norit) was added to the obtained light yellow solution, and the mixture was centrifuged at 23830 × g for 12 hours. The supernatant from the centrifuge was pressure filtered using a membrane filter with a pore size of 0.2 μm to obtain a light yellow transparent filtrate. The obtained filtrate was concentrated to 100 mL using a vacuum evaporator. The acetone solution was added to 800 mL of hexane in a 1000 mL conical beaker with stirring. The resulting white precipitate was filtered out using 5B filter paper, and the resulting solid was vacuum-dried. This yielded 64.40 g of a composition containing bismuth bonded to a phosphate ester as a white powder. Synthesis was confirmed using the aforementioned assay method.

[0249] <Example 1>

[0250] To 65 parts by mass of the bismuth-bonded phosphate-containing composition obtained in Production Example 1 (referred to as the "first bismuth compound" in the table) were added 12.9 parts by mass of methoxyethyl methacrylate (hereinafter referred to as "MEMA"), 6.6 parts by mass of tetrahydrofurfuryl acrylate (hereinafter referred to as "THFAA"), and 13.9 parts by mass of nonaethylene glycol dimethacrylate (hereinafter referred to as "9G") as polymerizable compounds. 1 part by mass of 2-methylimidazole was added as a coordinating organic compound. Furthermore, 0.6 parts by mass of methylstyrene dimer was added as another compounding agent and uniformly dissolved to obtain a curable composition. 0.9 parts by mass of 2,2'-azobis(2-methylbutyronitrile) (V-59) and 0.05 parts by mass of 1,1'-azobis(cyclohexane-1-carbonitrile) (V-40) were further added to the curable composition and completely dissolved. The curable composition was placed under reduced pressure using a vacuum pump to remove dissolved oxygen. The curable composition was injected into two glass molds fixed to a spacer with a 2 mm gap. The temperature was raised to a maximum of 90°C over 15 hours and then maintained at 90°C for 2 hours to allow polymerization, resulting in a pale yellow, transparent cured product. The yellowness index (YI) and odor per unit thickness of the resulting cured product were measured. The results are shown in Table 1, along with the pKa values of the coordinating organic compounds used.

[0251] <Example 2>

[0252] The same operation as in Example 1 was carried out except that 1 part by mass of dimethylaminoethyl methacrylate was used instead of 2-methylimidazole to obtain a light yellow transparent cured product.

[0253] <Example 3>

[0254] A pale yellow transparent cured product was obtained by the same operation as in Example 1 except that 1 part by mass of imidazole was used instead of 2-methylimidazole.

[0255] <Example 4>

[0256] A pale yellow transparent cured product was obtained by the same operation as in Example 1 except that 1 part by mass of pyrazole was used instead of 2-methylimidazole.

[0257] <Example 5>

[0258] The same operation as in Example 1 was carried out except that 1 part by mass of 4-methylimidazole was used instead of 2-methylimidazole to obtain a light yellow transparent cured product. The results are shown in Table 1.

[0259] <Example 6>

[0260] A pale yellow transparent cured product was obtained by the same operation as in Example 1 except that 1 part by mass of N-acetylimidazole was used instead of 2-methylimidazole.

[0261] <Example 7>

[0262] The same operation as in Example 1 was carried out except that 1 part by mass of triazole was used instead of 2-methylimidazole to obtain a light yellow transparent cured product. The results are shown in Table 1.

[0263] <Example 8>

[0264] The same operation as in Example 1 was carried out except that 1 part by mass of 1-vinylimidazole was used instead of 2-methylimidazole to obtain a light yellow transparent cured product. The results are shown in Table 1.

[0265] <Example 9>

[0266] A pale yellow transparent cured product was obtained by the same operation as in Example 1 except that 1 part by mass of 2-isopropylimidazole was used instead of 2-methylimidazole.

[0267] <Example 10>

[0268] The same operation as in Example 1 was carried out except that 1 part by mass of maleic acid was used in place of 2-methylimidazole in the form of maleic anhydride to obtain a pale yellow transparent cured product.

[0269] <Example 11>

[0270] The same operation as in Example 1 was carried out except that 1 part by mass of (trimethylsilyl)imidazole was used instead of 2-methylimidazole to obtain a light yellow transparent cured product. The results are shown in Table 1.

[0271] <Example 12>

[0272] A pale yellow transparent cured product was obtained by the same operation as in Example 1 except that 1 part by mass of benzimidazole was used instead of 2-methylimidazole.

[0273] <Example 13>

[0274] The same operation as in Example 1 was carried out except that 1 part by mass of allyl imidazole was used instead of 2-methyl imidazole to obtain a light yellow transparent cured product. The results are shown in Table 1.

[0275] <Example 14>

[0276] The same operation as in Example 1 was carried out except that 1 part by mass of 2-(tert-butylamino)ethyl methacrylate was used instead of 2-methylimidazole to obtain a light yellow transparent cured product.

[0277] <Example 15>

[0278] The same operation as in Example 1 was carried out except that 1 part by mass of methacrylic acid was used in the form of methacrylic anhydride instead of 2-methylimidazole to obtain a light yellow transparent cured product.

[0279] <Example 16>

[0280] A pale yellow transparent cured product was obtained by the same operation as in Example 1 except that 1 part by mass of 1,2-dimethylimidazole was used instead of 2-methylimidazole.

[0281] <Example 17>

[0282] A pale yellow transparent cured product was obtained by the same operation as in Example 1 except that 1 part by mass of 3,5-dimethylpyrazole was used instead of 2-methylimidazole.

[0283] <Example 18>

[0284] The same operation as in Example 1 was carried out except that 1 part by mass of carbazole was used instead of 2-methylimidazole to obtain a light yellow transparent cured product.

[0285] <Example 19>

[0286] The same operation as in Example 1 was carried out except that 1 part by mass of indole was used instead of 2-methylimidazole to obtain a light yellow transparent cured product. The results are shown in Table 1.

[0287] <Example 20>

[0288] To 65 parts by mass of the phosphate-bound bismuth-containing composition obtained in Production Example 1, 12.5 parts by mass of MEMA, 6.3 parts by mass of THFAA, and 13.6 parts by mass of 9G were added as polymerizable compounds. The same procedures as in Example 1 were followed, except that 1 part by mass of imidazole and 1 part by mass of maleic anhydride were added as coordinating organic compounds, to produce a pale yellow transparent cured product. The results are shown in Table 2.

[0289] <Example 21>

[0290] The results are shown in Table 2.

[0291] Comparative Example 1

[0292] To 65 parts by mass of the phosphate-bound bismuth-containing composition obtained in Production Example 1, 13 parts by mass of MEMA, 6.7 parts by mass of THFAA, and 14 parts by mass of 9G were added as polymerizable compounds. The same procedures as in Example 1 were followed, except that no coordinating organic compound was added and 0.3 parts by mass of methylstyrene dimer and 1 part by mass of α-methylstyrene were added as additional additives. A light yellow, transparent cured product having a thickness of 2.42 mm was obtained. The results are shown in Table 1.

[0293] Comparative Example 2

[0294] A pale yellow transparent cured product was obtained by the same operation as in Example 1 except that 1 part by mass of pyrazine was used instead of 2-methylimidazole.

[0295] <Evaluation Test>

[0296] [X-ray shielding capability measurement]

[0297] The X-ray shielding capability of the resulting cured products was evaluated as follows: the X-ray dose was measured in accordance with JIS T 61331-1, "Protective equipment against diagnostic X-rays - Part 1: Method for determining the attenuation characteristics of materials," and the lead equivalent was determined. The X-ray apparatus used was an MG-45 manufactured by YXLON International, with an X-ray tube voltage of 120 kV and a tube current of 12.5 mA. A 2.5 mm Al additional filter was used. The distance from the X-ray tube focus to the sample was 600 mm, and the distance from the sample to the measuring device was 900 mm. An ionization chamber dose rate meter (RAMTEC-Solo A4 probe manufactured by TOYOMEDIC CO., LTD.) was used as the measuring instrument. The X-ray shielding capability was evaluated as the lead equivalent (mmPb), which is the thickness (mm) of an equivalent lead plate. The cured products of all Examples and Comparative Examples had a lead equivalent of 0.10 ± 0.04 mmPb.

[0298] [Yellowness measurement]

[0299] The yellowness of the resulting cured product was measured using a ColourMeter SM-T45 manufactured by Suga Test Instruments Co., Ltd. The measured yellowness was divided by the thickness (mm) of the cured product to evaluate the yellowness per unit thickness. The results are shown in Tables 1 and 2. The thickness of the cured product was measured using a digital micrometer.

[0300] [Determination of odor intensity]

[0301] To evaluate the odor of the resulting solidified material, the odor intensity was measured using a portable odor detector XP-329m manufactured by NEW COSMOS ELECTRIC CO., LTD. First, the device was placed in a stationary position with the odor suction port facing upward, and a ring-shaped lens sample holder was fixed horizontally thereon using a clamp. When the convex surface of the lens was mounted on the ring-shaped sample holder with the convex surface facing downward, the suction port of the odor detector was aligned with the most convex part of the center of the lens (the lowest part of the lens in this orientation), and the gap between the lowest surface of the lens facing downward and the suction port of the odor detector was 5 mm. A pre-run was performed before mounting the lens, and when the value stabilized, the lens sample was mounted. The stopwatch was started at this time point, with the time set to 0 seconds, and the odor intensity displayed was read simultaneously. After 60 seconds, the odor intensity at that time point was read and the value at 0 seconds was subtracted from the value to obtain the odor intensity of the sample. After the measurement, the device was operated for more than 2 minutes after the sample was removed. After confirming that the value was stable, the next measurement was performed. The measurement was performed 5 times, and the average value was used as the measured value. The results are shown in Tables 1 and 2.

[0302] [ 1 H NMR determination]

[0303] The solidified product obtained in Example 3 was immersed in an organic solvent and 1 The extract components were quantitatively analyzed by H NMR measurement. First, the solidified product of Example 3 was crushed, and the fragments (1 g) were placed in a 9 mL vial tube. Dimethyl sulfoxide-d6 (1 g) was added and soaked for 3 days. The extract was then filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to obtain an extract. p-Chlorobenzaldehyde (1.0 g) was dissolved in the extract as an internal standard, and the solution was subjected to filtration. 1 H NMR analysis revealed a singlet peak at a chemical shift of 10.00 ppm, originating from p-chlorobenzaldehyde, and a singlet peak at a chemical shift of 1.36 ppm, originating from the tert-butyl group of BHT. The ratio of these integrated values was 1:0.05881. Based on this result and the weight of the internal standard, the BHT concentration in the extract was calculated to be 7.3 ppm.

[0304] [GC / MS measurement]

[0305] The solidified material obtained in Example 3 was quantitatively analyzed for odor components by GC / MS analysis and NMR analysis. An Agilent 7890B was used for GC, an Agilent 597×MSD was used for MS, an Agilent 7697A was used for headspace sampler, and an Agilent 19091S-433HP-5ms was used for chromatographic column analysis (all manufactured by Agilent Technologies, Inc.). The solidified material from Example 3 was pulverized, and the fragments (1 g) were placed in a 10 mL dedicated vial. After equilibration at 90°C for 30 minutes using the headspace sampler, the volatile components were introduced into the GC / MS at a flow rate of 2.1 mL / min with a column oven temperature of 250°C. The results showed that a phenol peak was observed at a retention time of 2.78 minutes, and a BHT peak was observed at a retention time of 5.04 minutes. The peak intensity ratio of phenol to BHT was 1.59. The peak intensity ratio of the two volatile components obtained by GC / MS is consistent with their content ratio in the solidified product. 1 The BHT content in the cured product was 7.3 ppm as determined by H NMR, and the phenol to BHT peak intensity ratio by GC / MS was 1.59, so the phenol content was calculated. The result showed that the phenol content in the cured product of Example 3 was 4.6 ppm. The GC / MS spectrum of the cured product of Example 3 is shown in FIG. Figure 1 .

[0306] [Determination of phenol volatile content]

[0307] The solidified material obtained in Example 3 was placed in a 10 cm square polyethylene bag with a ziplock and allowed to stand for 1 minute. The concentration of phenol volatilized from the polyethylene bag was then measured using a phenol gas detector tube. The concentration of phenol volatilized from the solidified material in Example 3 was 5 ppm.

[0308] [Table 1]

[0309]

[0310] [Table 2]

[0311]

[0312] From the above results, it is understood that a solidified product with low odor can be obtained by using a coordinating organic compound having an acid dissociation constant pKa of 1.5 or more.

[0313] Furthermore, it was found that by using a coordinating organic compound having an acid dissociation constant pKa within a range of 2.0 to 15.0, a cured product having a lower YI, that is, yellow tint, and a lower odor than an unused cured product can be obtained.

Claims

1. A composition comprising: a first bismuth compound having bismuth and at least one of an acryloyl group and a methacryloyl group; and A coordinating organic compound with an acid dissociation constant pKa of 1.5 or greater.

2. The composition according to claim 1, wherein The acid dissociation constant pKa of the coordinating organic compound is 2.0 or more and 15.0 or less.

3. The composition according to claim 1, wherein A ratio M1 / M2 of a mass M1 of the first bismuth compound to a mass M2 of the coordinating organic compound is 4 or more and 4990 or less.

4. The composition according to claim 1, wherein The coordinating organic compound includes at least one selected from the group consisting of a compound having an imidazole skeleton, a compound having a pyrazole skeleton, a compound having a triazole skeleton, and a compound having a tetrazole skeleton.

5. The composition according to claim 1, wherein The coordinating organic compound includes a compound having at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and an unsaturated bond.

6. The composition according to claim 1, wherein The coordinating organic compound includes an unsaturated dicarboxylic acid.

7. The composition according to claim 1, wherein The coordinating organic compound comprises an unsaturated carboxylic acid ester.

8. The composition according to claim 1, wherein The coordinating organic compound includes an unsaturated carboxylic acid anhydride.

9. The composition according to claim 1, wherein The coordinating organic compound comprises a compound selected from imidazole, 1-vinylimidazole, 1-allylimidazole, N-acetylimidazole, trimethylsilylimidazole, pyrazole, triazole, 1H-tetrazole, 1,2,3-benzotriazole, benzimidazole, allyl isonicotinate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, indole, carbazole, 2-methylimidazole, 4-methylimidazole, 1,2,3-benzotriazole, At least one compound selected from the group consisting of 2-benzisothiazol-3(2H)-one, 2-isopropylimidazole, 1,2-dimethylimidazole, levomenthol, piperonal, triallyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, 2-(tert-butylamino)ethyl methacrylate, 4-acryloylmorpholine, triacryloylhexahydrotriazine, dimethylpyrazole, linalool, camphor, acrylic acid, methacrylic acid, maleic acid, acrylic anhydride, methacrylic anhydride, and maleic anhydride.

10. The composition according to claim 1, wherein The first bismuth compound further has a phosphate bond.

11. The composition according to claim 1, wherein The first bismuth compound further has a phenyl group.

12. A curable composition comprising: The composition according to any one of claims 1 to 11; and The first polymerizable compound has at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

13. The curable composition according to claim 12, wherein The total content of the first bismuth compound and the coordinating organic compound is 10% by mass or more and 90% by mass or less.

14. A cured product, which is a cured product of the curable composition according to claim 12.

15. An optical article comprising the cured product according to claim 14. A lens comprising the cured product according to claim 14 .

17. Spectacles comprising the lens according to claim 16.

18. An antibacterial / antiviral agent comprising the cured product according to claim 14.

19. A resin composition comprising bismuth and a (meth)acrylic resin. The phenol content determined by gas chromatography-mass spectrometry using the polymerization inhibitor present inside as a reference was 10 ppm or less.

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